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| United States Patent |
5,216,009
|
|
Fujimoto
, et al.
|
June 1, 1993
|
Method for controlling Nilaparvata lugens
Abstract
A method for controlling insect pests which belong to Homoptera which
comprises applying an insect pesticidally effective amount of the conpound
having the formula:
##STR1##
wherein A is a phenyl group, a 3-fluorophenyl group, a 3-chlorophenyl
group and 3,5-difluorophenyl group; X is an oxygen atom or a methylene
group, optionally together with an additive(s) and/or an inert carrier(s)
to the said insect pests and/or the locus where the said insect pests
propagage and/or cultivated plants to which the said insect pests do
damage.
| Inventors:
|
Fujimoto; Hiroaki (Osaka, JP);
Shuto; Akira (Hyogo, JP);
Sakamoto; Noriyasu (Hyogo, JP);
Kisida; Hirosi (Hyogo, JP);
Matsuo; Noritada (Hyogo, JP);
Umeda; Kimitoshi (Osaka, JP)
|
| Assignee:
|
Sumitomo Chemical Company, Limited (Osaka, JP)
|
| Appl. No.:
|
878525 |
| Filed:
|
May 5, 1992 |
Foreign Application Priority Data
| May 10, 1991[JP] | 3-105753 |
| May 10, 1991[JP] | 3-135821 |
| Current U.S. Class: |
514/406; 424/405; 424/421 |
| Intern'l Class: |
A01N 043/56; A01N 025/14 |
| Field of Search: |
424/405
514/406
|
References Cited
U.S. Patent Documents
| 4943586 | Jul., 1990 | Bowers et al. | 514/406.
|
| Foreign Patent Documents |
| 0376598 | Jul., 1990 | EP.
| |
Other References
European Search Report.
|
Primary Examiner: Page; Thurman K.
Assistant Examiner: Levy; Neil
Attorney, Agent or Firm: Birch, Stewart, Kolasch & Birch
Claims
What is claimed is:
1. A method for controlling Nilaparvata lugens which comprises applying
1-[3-(2-chloro-4-phenoxy-phenoxy)propyl]pyrazole at an amount of from
0.001 g to 500 g per 10 ares to the said insect pests and/or rice plants.
2. A method for controlling Nilaparvata lugens which comprises applying
1-[3-{2-chloro-4-(3-fluorophenoxy)-phenoxy}propyl]pyrazole at an amount of
from 0.001 g to 500 g per 10 ares to the said insect pests and/or rice
plants.
3. A method for controlling Nilaparvata lugens which comprises applying
1-[3-{2-chloro-4-(3-chlorophenoxy)-phenoxy}propyl]pyrazole at an amount of
from 0.001 g to 500 g per 10 ares to the said insect pests and/or rice
plants.
4. A method for controlling Nilaparvata lugens which comprises applying
1-[3-{2-chloro-4-(3,5-difluorophenoxy)phenoxy}propyl]pyrazole at an amount
of from 0.001 g to 500 g per areas to the said insect pests and/or rice
plants.
5. A method for controlling Nilaparvata lugens which comprises applying
1-[3-(2-chloro-4-benzylphenoxy)-propyl]pyrazole at an amount of from 0.001
g to 500 g per 10 ares to the said insect pests and/or rice plants.
6. A method for controlling Nilaparvata lugens which comprises applying
1-[3-{2-chloro-4-(3-fluorobenzyl)-phenoxy}propyl]pyrazole at an amount of
from 0.001 g to 500 g per 10 ares to the said insect pests and/or rice
plants.
7. A method for controlling Nilaparvata lugens which comprises applying
1-[3-{2-chloro-4-(3-chlorobenzyl)-phenoxy}propyl]pyrazole at an amount of
from 0.001 g to 500 g per areas to the said insect pests and/or rice
plants.
8. A method for controlling Nilaparvata lugens which comprises applying
1-[3-{2-chloro-4-(3,5-difluorobenzyl)phenoxyl}propyl]pyrazole at an amount
of from 0.001 g to 500 g per 10 ares to the said insect pests and/or rice
plants.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method for controlling insect pests
which belong to Homoptera.
2. Description of the Prior Art
It is described in U.S. Pat. No. 4,943,586 and European Patents Application
No. 376,598 that certain pyrazole compounds are useful as insect
pesticides.
It is very difficult to control insect pests which belong to Homoptera such
as planthoppers, leafhoppers, aphids and whiteflies by reason of their
specific ecological and physiological traits of character and furthermore
very rapid development of drug-resistant system. So there are very severe
damages in practical productions on Agriculture. However, there are few
methods to effectively control such insect pests.
OBJECT OF THE INVENTION
As a result of the extensive study seeking method for effectively
controlling such insect pests, it has been found that the following method
exhibits a remarkable high controlling effect.
The main object of the present invention is to provide an improved method
for controlling insect pests belonging to Homoptera.
This object as well as other objects and advantages of the present
invention will become apparent to those skilled in the art from the
following description.
SUMMARY OF THE INVENTION
The present invention relates to a method for controlling insect pests
which belong to Homoptera which comprises applying an insect pesticidally
effective amount of the compound having the formula:
##STR2##
wherein A is a phenyl group, a 3-fluorophenyl group, a 3-chlorophenyl
group and 3,5-difluorophenyl group; X is an oxygen atom or a methylene
group, optionally together with an additive(s) and/or an inert carrier(s)
to the said insect pests and/or the locus where the said insect pests
propagate and/or cultivated plants to which the said insect pests do
damage.
DETAILED DESCRIPTION OF THE INVENTION
The 4-substituted-2-chlorophenoxypropylpyrazole compounds (I) used as an
active ingredient in the method of the present invention have an excellent
juvenile hormone-like activity against insect pests which belong to
Homoptera such as planthoppers, leafhoppers, aphids and whiteflies. They
exhibit various strong actions such as metamorphosis inhibition,
embryogenesis inhibition and sterilization and are thus efficacious as
growth regulators, chemosterilants, ovicides or reproduction inhibitory
agents on various insect pests which belong to Homoptera such as
planthoppers, leafhoppers, aphids and whiteflies. They are also
efficacious against insect pests having an increased resistance to
commercial insecticides.
Among the 4-substituted-2-chlorophenoxypropylpyrazole compounds (I) as an
active ingredient, preferred are those wherein X is an oxygen atom.
Examples of the insect pests which belong to Homoptera against which the
method of the present invention exhibits controlling effects are as shown
below.
Planthoppers such as brown rice planthopper (Nilaparvata lugents), small
brown planthopper (Laodelphax striatellus) and whitebacked rice
planthopper (Sogatella furcifera); leafhoppers such as green rice
leafhoppers (Nephotettix cincticeps, Nephotettix virescens, Nephotettix
nigropictus and Nephotettix malayanus), zig-zag rice leafhopper (Recilia
dorsalis, grape leafhopper (Arboridia apicalis) and tea green leafhopper
(Empoasca onukii); white flies such as greenhouse whitefly (Trialeurodes
vaporariorum), sweet potato whitefly (Bemisia tabaci) and citrus spiny
whitefly (Aleurocanthus spiniferus); aphids such as cotton aphid (Aphis
gossypii), spiraea aphid (Aphis citricola), green peach aphid (Myzus
persicae) and foxglove aphid (Aulacorthum solani).
Among the insect pests which belong to Homoptera as above exemplified, the
method of the present invention is particularly effective in controlling
those belong to genera such as Nilaparvata, Nephotetti, Trialeurodes,
Bemisia and Aphis, and also exhibit a remarkable controlling effect on
brown rice planthopper (Nilaparvata lugens), green rice leafhopper
(Nephotettix cincticeps), greenhouse whitefly (Trialeurodes vaporariorum),
sweet potato whitefly (Bemisia tabaci) and cotton aphid (Aphis gossypii).
In the method of the present invention, examples of cultivated plants are
rice plants, vegetables, cottons, fruits and flowers, etc. Among the
cultivated plants, the method of the present invention is most
particularly effective in rice plants cultivated in a paddy field, to
which the insect pests do most severe damage.
The method of the present invention may be used in mixtures of the
4-substituted-2-chlorophenoxypropylpyrazole compounds (I) as the active
ingredient and other insecticides and/or acaricides to enhance or expand
their insecticidal or pesticidal use.
Examples of the other insecticides and/or acaricide include
organophosphorus compounds (e.g. fenitrothion (O,O-dimethyl
O-(3-methyl-4-nitrophenyl)phosphorothioate), fenthion (O,O-dimethyl
O-[3-methyl-4-(methylthio)phenyl]phosphorothioate), diazinon
(O,O-diethyl-O-(2-isopropyl-6-methyl-pyrimidin-4-yl)phosphorothioate),
chlorpyrifos (O,O-diethyl-O-(3,5,6-trichloro-2-pyridyl)phosphorothioate),
acephate (O,S-dimethyl acetylphosphoramidothioate), methidathion
(S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl
O,O-dimethylphosphorodithioate), disulfoton (O,O-diethyl
S-2-ethylthioethyl phosphorothioate), DDVP
(2,2-dichlorovinyldimethylphosphate), sulprofos (O-ethyl
O-4-(methylthio)phenyl S-propyl phosphorodithioate), cyanophos
(O-4-cyanophenyl O,O-dimethyl phosphorothioate), dioxabenzofos
(2-methoxy-4H-1,3,2-benzodioxaphosphinine-2-sulphide), dimethoate
(O,O-diethyl-S-(N-methylcarbamoylmethyl)dithiophosphate), phenthoate
(ethyl 2-dimethoxyphosphinothioylthio(phenyl)acetate), malathion (diethyl
(dimethoxyphosphinothioylthio)succinate), trichlorfon (dimethyl
2,2,2-trichloro-1-hydroxyethylphosphonate), azinphos-methyl
(S-3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-ylmethyl
O,O-dimethylphosphoro-dithioate) and monocrotophos (dimethyl
(E)-1-methyl-2-(methylcarbamoyl)vinyl phosphate), etc.); carbamate
derivatives (e.g. BPMC (2-sec-butylphenyl methylcarbamate), benfuracarb
(ethyl
N-[2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl(methyl)aminothio]-N-
isopropyl-beta-alaninate), propoxur (2-isopropoxyphenyl N-methylcarbamate),
carbosulfan (2,3-dihydro-2,2-dimethyl-7-benzo[b]furanyl
N-methylcarbamate), carbaryl (1-naphthyl-N-methylcarbamate), methomyl
(S-methyl-N-[(methylcarbamoyl)oxy]thioacetimidate), ethiofencarb
(2-(ethylthiomethyl)phenyl methylcarbamate), aldicarb
(2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime) and Oxamyl
(N,N-dimethyl-2-methylcarbamoyl-oxyimino-2-(methylthio)acetamide), etc.);
pyrethroides (e.g. ethofenprop
(2-(4-ethoxyphenyl-2-methylpropyl-3-phenoxybenzylether), fenvalerate
((RS)-alpha-cyano-3-phenoxybenzyl
(RS)-2-(4-chlorophenyl)-3-methylbutyrate), esfenvalerate
((S)-alpha-cyano-3-phenoxybenzyl (S)-2-(4-chlorophenyl)-3-methylbutyrate),
fenpropathrin ((RS)-alpha-cyano-3-phenoxybenzyl
2,2,3,3-tetramethylcyclopropanecarboxylate), cypermethrin
((RS)-alpha-cyano-3-phenoxybenzyl
(1RS,3RS)-(1RS,3-RS)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxy
late), permethrin (3-phenoxybenzyl
(1RS,3RS)-(1RS,3-RS)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxy
late), cyhalothrin ((R,S)-alpha-cyano-3-phenoxybenzyl
(Z)-(1RS,3RS)-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropan
ecarboxylate), deltamethrin ((S)-alphacyano-m-phenoxybenzyl
(1R,3R)-3-(2,2-dibromovinyl)-2-dimethylcyclopropanecarboxylate) and
cycloprothrin ((RS)-alpha-cyano-3-phenoxybenzyl
(RS)-2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylate), etc.);
thiadiazine derivatives (e.g. buprofezin
(2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-triadiazin-4-one), etc.);
nitroimidazolidine derivatives (e.g. imidacloprid
(1-(6-chloro-3-pyridylmethyl)-N-nitro-imidazolidin-2-ylideneamine), etc.);
nereistoxin derivatives (e.g. cartap (S,S'-(2-dimethylaminotrimethylene)
bis(thiocarbamate), thiocyclam (N,N-dimethyl-1,2,3-trithian-5-ylamine) and
bensultap (S,S'-2-dimethylaminotrimethylene di(benzenethiosulphonate),
etc.); halogenated hydrocarbons (e.g. endosulfan
(6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzod
ioxathiepin-3-oxide) and gamma-BHC (1,2,3,4,5,6-hexachlorocyclohexane),
etc.); benzoylphenylurea derivatives (e.g. chlorfluazuron
(1-[3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridin-2-yloxy)phehyl]-3-(2
,6-difluorobenzoyl)urea), teflubenzuron
(1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea) and
flufenoxuron
(1-[4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl]-3-(2,6-difluorob
enzoyl)urea, etc.); formamidine derivatives (e.g. amitraz
(N,N'-[(methylimino)dimethylidyne]-di-2,4-xylidine) and chlordimeform
(N'-(4-chloro-2-methylphenyl)-N,N-dimethylmethanimidamide), etc.).
On the practical use of the method of the present invention, the
4-substituted-2-chlorophenoxypropylpyrazole compound (I) as the active
ingredient may be employed as such but are normally mixed with appropriate
additives such as solid carriers, liquid carriers, gaseous carriers, feed,
etc. to formulate their compositions. When desired or necessary,
surfactants and other adjuvants may be further incorporated therein. The
compositions may be prepared into any conventional forms such as oil
sprays, emulsifiable concentrates, wettable powders, flowable concentrates
(e.g. water-based suspension formulations, water-based emulsion
formulations), granules, dusts, aerosals, heating smoking formulations
(e.g. self-burning-type smoking formulations, chemical reaction-type
smoking formulations, porous ceramic plate-type smoking formulations), ULV
formulations, poison baits, etc.
The composition used in the method of the present invention contains
generally the 4-substituted-2-chlorophenoxypropylpyrazole compound(s) (I)
as the active ingredient in an amount of from about 0.001% to 95% by
weight based on the composition.
Examples of the solid carrier usable for making the composition are fine
powders or granules of clays (e.g. kaolin clay, diatomaceous earth,
synthetic hydrated silica, bentonite, Fubasami clay, terra alba), talc,
ceramics, other inorganic minerals (e.g. sericite, quartz, sulfur,
activated carbon, calcium carbonate, hydrated silica), chemical
fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate,
urea, ammonium chloride), etc. Examples of the liquid carrier include
water, alcohols (e.g. methanol, ethanol), ketones (e.g. acetone, methyl
ethyl ketone), aromatic hydrocarbons (e.g. benzene, toluene, xylene,
ethylbenzene, methylnaphthalene), aliphatic hydrocarbons (e.g. hexane,
cyclohexane, kerosene, gas oil), esters (e.g. ethyl acetate, butyl
acetate), nitriles (e.g. acetonitriles, isobutyronitrile), ethers (e.g.
diisopropyl ether, dioxane), acid amides (e.g. N,N-dimethylformamide,
N,N-dimethylacetamide), halogenated hydrocarbons (e.g. dichloromethane,
trichloroethane, carbon tetrachloride), dimethylsulfoxide, vegetable oils
(e.g. soybean oil, cotton seed oil), etc. Examples of the gaseous carrier,
i.e. a propellant, include freon gas, butane gas, LPG (liquefied petroleum
gas), dimethyl ether, carbon dioxide, etc.
Examples of the surfactant are alkylsulfates, alkylsulfonates,
alkylarylsulfonates, alkyl aryl ethers and polyoxyethylene derivatives
thereof, polyethylene glycol ethers, polyvalent alcohol esters, sugar
alcohol derivatives, etc. Examples of the adjuvants such as binders and
dispersing agents are casein, gelatin, polysaccharides (e.g. starch
powders, gum arabic, cellulose derivatives, alginic acid), lignin
derivatives, bentonite, sugars, synthetic water-soluble high molecular
weight substances (e.g. polyacrylic alcohol, polyvinylpyrrolidone,
polyacrylic acid), etc. Examples of the stabilizer include PAP (acidic
isopropyl phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (mixture
of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol),
vegetable oils, mineral oils, surfactants, fatty acids or esters thereof,
etc.
The base material for self-burning-type smoking formulations may include,
for example, burning heat-generating agents such as nitrates, nitrites,
guanidine salts, potassium chlorate, nitrocellulose, ethyl cellulose and
wood powders, pyrolysis-promoting agents such as alkali metal salts,
alkaline earth metal salts, dichromates and chromates, oxygen-supplying
agents such as potassium nitrate, burning-supporting agents such as
melamine and wheat starch, extenders such as diatomaceous earth, binders
such as synthetic pastes, etc. The base material for chemical
reaction-type smoking formulations can include, for example,
heat-generating agents such as alkali metal sulfides, alkali metal
polysulfides, alkali metal hydrosulfides, hydrated salts of alkali metals
and calcium oxide, catalyzing agents such as carbonaceous substances, iron
carbide and activated clay, organic foaming agents such as
azodicarbonamide, benzenesulfonyl hydrazides,
dinitrosopentamethylenetetramine, polystyrene and polyurethane, fillers
such as natural fiber pieces and synthetic fiber pieces, etc. The base
material for poison baits may contain feed components such as crop
powders, essential vegetable oil, sugars and crystalline cellulose,
antioxidants such as dibutylhydroxyrtolune and nordihydroguaiaretic acid,
preservatives such as dehydroacetic acid, feeding error preventing agnets
such as red paper powders, incentive flavors such as cheese flavor and
onion flavor, etc.
Flowable concentrates (water-based suspension or emulsion formulations) are
generally obtained by dispersing about 1 to 75 parts by weight of the
4-substituted-2-chlorophenoxypropylpyrazole compound (I) as the active
ingredient finely and uniformly into water containing about 0.5 to 15
parts by weight of a dipersing agent, about 0.1 to 10 parts by weight of a
suspending agent (e.g. protective colloids, compounds giving a thixotropic
property) and optionally about 0 to 10 parts by weight of an auxiliary
agent(s) such as a defoaming agent, an anticorrosive agent, a stabilizing
agent, a spreading agents, penetration auxiliaries, antifreezing agent, an
antibacterial agent, an antimolding agent and the like. The use of an oil,
into which the active ingredient is hardly soluble, in place of water
affords oil-based suspension formulations. Examples of the protective
colloids as above mentioned are gelatin, casein, gums, cellulose ethers,
polyvinyl alcohol, etc. Examples of the compounds giving a thixotropic
property are bentonite, aluminum magnesium silicate, xanthane gum,
polyacrylic acid, etc.
The composition of the invention thus obtained may be used as such or after
diluting with water. It may be also used in a mixture with any other
active component or composition chosen from insecticides, nematocides,
acaricides, fungicides, bacteriocides, herbicides, plant growth
regulators, synergistic agents, fertilizers, soil conditioners, animal
feed, etc. Alternatively, the composition of the invention may be applied
separately but simultaneously with said other active component or
composition.
For the purpose of controlling insect pests in the agricultural field, the
4-substituted-2-chlorophenoxypropylpyrazole compound (I) as the active
ingredient according to the method of the present invention may be applied
to the insect pests or the locus where the insect pests propagate
generally in an amount of about 0.001 g to 500 g, and preferably about 0.1
g to 500 g per 10 ares. when the
4-substituted-2-chlorophenoxypropylpyrazole compound (I) as the active
ingredient is applied in a form of emulsifiable concentrate, wettable
powder, flowable concentrate or the like after dilution with water, its
concentration may be from about 0.0001 to 1000 ppm. Granules, dusts, etc.
may be used as such, i.e. without water dilution. When the
4-substituted-2-chlorophenoxypropylpyrazole compound (I) as the active
ingredient is used for household or public hygiene, it may be used in the
form of emulsifiable concentrate, wettable powder, flowable concentrate or
the like with water dilution, etc. In this case, the concentration of the
active ingredient may be from about 0.0001 to 10,000 ppm. In case of oils,
aerosol, fumigants, ULV formulations, poison baits, etc., they may be
applied as such. However, the doses and concentrations may vary within
broad ranges depending upon the composition, the application time, the
place applied, the application method, the kind of insect pests, the
condition of damage, etc. and may be increased or decreased, irrespective
of the general ranges set forth above.
The 4-substituted-2-chlorophenoxypropylpyrazole compound (I) as the active
ingredient in the method of the present invention can be produced by
various processes, among which typical examples in the same manner as
described in European Patents Application No. 376,598 are shown below.
The 4-substituted-2-chlorophenoxypropylpyrazole compound (I) is produced by
reacting a compound having the formula:
##STR3##
wherein B is a halogen atom, a methanesulfonyloxy group or a
toluenesulfonyloxy group; R and X are each as defined above, with
1,2-pyrazole in the presence of a deoxidation agent. The reaction is
ordinarily carried out with or without an inert solvent at a temperature
of from about -30.degree. C. to about 200.degree. C., preferably from
about 0.degree. C. to about 110.degree. C. for from about 0.5 hour to
about 30 hours.
The molar proportion of the compound (II) and 1,2-pyrazole to be used for
the reaction is ordinary to be from 1:0.1 to 1:10, preferably to be from
1:0.8 to 1:1.2. Examples of the inert solvent are N,N-dimethylformamide,
dimethylsulfoxide, tetrahydrofuran, toluene, 1,2-dimethylethane,
dimethylacetoamide, etc. Examples of the deoxidation agent are alkali
methals, alkali methal hydrides, alkali methal amides, alkali methal
hydoxides, alkali methal carbonates and organic bases (e.g.
4-dimethylaminopyridine), etc.
When necessary or desired, an ammonium salt such as
triethylbenzylbenzylammonium chloride and tetrabutylammonium bromide or an
amine such as tris(3,6-dioxaheptyl) amine may be added to the reaction
system as a catalyst. When the above catalyst is added to the reaction
system, water or two layer mixtures of water and an organic solvent(s) may
be used as the inert solvent.
After completion of the reaction, post-treatment may follow in a per se
conventional manner such as extraction with an organic solvent and
concentration. When necessary or desired, the product may further be
purified by chromatography, distillation, recrystallization, etc.
Among the starting compounds in the above processes, the compound (II)
wherein B is a halogen atom can be prepared from a phenol compound having
the formula:
##STR4##
wherein A and X are each as defined above by the known method as described
in Org. Synth., I, 435 (1932), etc. The compound (II) wherein B is a
mathanesulfonyloxy group can be prepared from an alcohol compound having
the formula:
##STR5##
wherein A and X are each as defined above according to the method as
described in U.S. Pat. No. 4,943,586.
Further, the compound (II) wherein B is a halogen atom can be also prepared
from the alcohol compound (IV) according to the method as described in J.
Amer. Chem. Soc., 68, 2513 (1946), J. Org. Chem., 14, 706 (1949), etc.
The phenol compound (III) can be prepared by reacting a corresponding
non-chlorinated compound, i.e. a phenol compound, having the formula:
##STR6##
wherein A and Z are each as defined above, with a chlorinating agent by
the known method as described in J. Amer. Chem., 73, 2723 (1951), J. Org.
Chem., 39, 1160 (1974), etc.
The molar proportion of the phenol compound (IV) and the chlorinating agent
is not limitative but it is ordinary to use the chlorinating agent in an
amount equivalent to the phenol compound (IV) or somewhat in excess.
Examples of the chlorinating agent are chlorine, tert-butyl hypochlorite,
sulfuryl chloride, etc. If necessary and desired, the reaction can be
carried out in the presence of an inert solvent. Examples of the solvent
are dichloromethane, 1,2-dichloroethane, carbon tetrachloride, benzene,
acetic acid, etc. The chlorinating agent itself may be available as a
reaction medium when it is liquid. The reaction temperature is usually
from about -80.degree. C. to the refluxing temperature of the reaction
system, preferably from about -20.degree. C. to the refluxing temperature
of the reaction system.
After completion of the reaction, post-treatment may follow in a per se
conventional manner such as extraction with an organic solvent and
concentration. When necessary or desired, the product may further be
purified by chromatography, distillation, recrystallization, etc.
The phenol compound (IV) and 1,2-pyrazole are available on the commercial
market or can be readily produced from appropriate commercial products by
conventional method.
Practical and presently preferred embodiments of the invention will be
hereinafter explained in more detail referring to Formulation Examples,
Test Examples and Production Examples of the
4-substituted-2-chlorophenoxypropylpyrazole compound (I) as the active
ingredient.
These examples, however, should not be construed to be limitative.
In the following Production Examples, % is by weight unless otherwise
indicated.
PRODUCTION EXAMPLE (OF THE ACTIVE INGREDIENT) 1
Production of the Compound No. 3
To a mixture of 5 ml of anhydrous N,N-dimethylformamide and 52 mg of sodium
hydride (60% oily suspension), there was added 84 mg of pyrazole with
stirring. After 30 minutes, a solution of 463 mg of
3-[2-chloro-4-(3-chlorophenoxy)phenoxy]propylbromide in 5 ml of anhydrous
N,N-dimethylformamide was added thereto at room temperature, followed by
stirring at the same temperature for 5 hours.
The reaction mixture was diluted with 50 ml of ethyl acetate. The diluted
mixture was washed twice with 30 ml of a saturated aqueous solution of
ammonium chloride, dried over anhydrous magnesium sulfate and concentrated
under reduced pressure. The residue was subjected to silica gel
chromatography to give 340 mg of
1-[3-{2-chloro-4-(3-chlorophenoxy)phenoxy}propyl]pyrazole as a colorless
oily substance. Yield: 76%, n.sup.23.9.sub.D :1.5879.
PRODUCTION EXAMPLE (OF THE ACTIVE INGREDIENT) 2
Production of Compound No. 4
To a mixture of 5 ml of anhydrous N,N-dimethylformamide and 42 mg of sodium
hydride (60% oily suspension), there was added 79 mg of pyrazole with
stirring. After 30 minutes, a solution of 400 mg of
3-[2-chloro-4-(3,5-difluorophenoxy)phenoxy]propylbromide in 5 ml of
anhydrous N,N-dimethylformamide was added thereto at room temperature,
followed by stirring at the same temperature for 5 hours.
The reaction mixture was diluted with 50 ml of ethyl acetate. The diluted
mixture was washed twice with a saturated aqueous solution of ammonium
chloride, dried over anhydrous magnesium sulfate and concentrated under
reduced pressure. The residue was subjected to silica gel chromatography
to give 317 mg of
1-[3-{2-chloro-4-(3,5-difluorophenoxy)phenoxy}propyl]pyrazole as a
colorless oily substance. Yield: 82%, n.sup.24.1.sub.D :1.5535.
PRODUCTION EXAMPLE (OF THE ACTIVE INGREDIENT) 3
Production of Compound No. 7
To a mixture of 5 ml of anhydrous N,N-dimethylformamide and 34 mg of sodium
hydride (60% oily suspension), there was added 57 mg of pyrazole with
stirring. After 30 minutes, a solution of 300 mg of
3-[2-chloro-4-(3-chlorobenzyl)phenoxy]propylbromide in 5 ml of anhydrous
N,N-dimethylsulfoxide was added thereto at room temperature, followed by
stirring at the same temperature for 5 hours.
The reaction mixture was diluted with 50 ml of ethyl acetate. The diluted
mixture was washed twice with a saturated aqueous solution of ammonium
chloride, dried over anhydrous magnesium sulfate and concentrated under
reduced pressure. The residue was subjected to silica gel chromatography
to give 197 mg of 1-[3-{2-chloro-4-(3-chlorobenzyl)phenoxy}propyl]pyrazole
as a colorless oily substance. Yield: 68%, m.p.: 52.5.degree. C. Some
examples of the 4-substituted-2-chlorophenoxypropylpyrazole compound (I)
as the active ingredient were produced in the same manner as described
above and shown in Table 1.
TABLE 1
__________________________________________________________________________
Compound Physical
No. Chemical structure constant
__________________________________________________________________________
##STR7## n.sub.D.sup.22.9 1.5855
2
##STR8## n.sub.D.sup.24.1 1.5729
3
##STR9## n.sub.D.sup.23.9 1.5879
4
##STR10## n.sub.D.sup. 24.2 1.5535
5
##STR11## n.sub.D.sup.24.2 1.5842
6
##STR12## m.p. 45.1.degree. C.
7
##STR13## m.p. 52.5.degree. C.
8
##STR14## n.sub.D.sup.22.7 1.5817
__________________________________________________________________________
In Formulation Examples as set forth below, parts and % are all by weight.
The compound numbers correspond to those as shown in Table 1.
FORMULATION EXAMPLE 1
Emulsifiable Concentrate
To a solution of 10 parts of each of Compounds Nos. 1 to 8 in 35 parts of
xylene and 35 parts of dimethylformamide, 14 parts of polyoxyethylene
styrylphenyl ether and 6 parts of calcium dodecylbenzenesulfonate are
added, and the resultant mixture is thoroughly mixed while stirring to
give an emulsifiable concentrate containing the active ingredient in 10%.
FORMULATION EXAMPLE 2
Wettable Powder
Twenty parts of each of Compounds Nos. 1 to 8 are added to a mixture of 4
parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20
parts of fine powders of synthetic hydrated silica and 54 parts of
diatomaceous earth, and the resultant mixture is stirred in a mixer to
give a wettable powder containing the active ingredient in 20%.
FORMULATION EXAMPLE 3
Granules
Five parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 60
parts of clay are added to 5 parts of each of Compound Nos. 1, 2, 3, 4, 5
and 8, and the resultant mixture is pulverized and kneaded with a suitable
amount of water. The mixture is granulated in a granulator and air-dried
to give granules containing the active ingredient in 5%.
FORMULATION EXAMPLE 4
Granules
Five parts of fine powders of synthetic hydrated silica, 5 parts of sodium
dodecylbenzenesulfonate, 30 parts of bentonite and 55 parts of clay are
added to 5 part of each of Compound Nos. 6 and 7, and the resultant
mixture is pulverized and kneaded with a suitable amount of water. The
mixture is granulated in a granulator and air-dried to give granules
containing the active ingredient in 5%.
FORMULATION EXAMPLE 5
Dusts
To a mixture of 1 part of fine powders of synthetic hydrated silica, 1 part
of an aggregating agent ("Driless B" manufactured by Sankyo Co., Ltd.) and
7.7 parts of clay, 0.3 part of each of Compound Nos. 1, 2, 3, 4, 5 and 8
is added, and the resultant mixture is well pestled in a mortar and
further stirred in a mixer. To the thus obtained mixture, there are added
90 parts of cut clay, followed by mixing to give dusts containing the
active ingredient in 0.3.
FORMULATION EXAMPLE 6
Dusts
A mixture of 0.3 part of each of Compound Nos. 6 and 7 and 0.03 part of
fine powders of synthetic hydrated silica is stirred well in a mixer and
pulverized by the aid of a centrifugal pulverizer. To the resultant
mixture, 0.97 part of fine powders of synthetic hydrated silica, 1 part of
"Driless B" and 7.7 parts of clay are added, and the resulting mixture is
pestled in a mortar and stirred in a mixer. Ninety parts of cut clay are
added thereto, and further mixing is effected in a sack to give dusts
containing the active ingredient in 0.3%.
FORMULATION EXAMPLE 7
Dusts
A mixture of 0.3 part of each of Compound Nos. 1, 2, 3, 4, 5 and 8, 2 parts
of fenitrothion (O,O-dimethyl O-(3-methyl-4-nitrophenyl)phosphorothioate
as an organophosphorus insecticide, 3 parts of fine powders of synthetic
hydrated silica, 1 part of "Driless B" and 3.7 parts of clay are pestled
in a mortar and stirred in a mixer. Then, 90 parts of cut clay are added
thereto, and the resultant mixture is further mixed in a sack to give
dusts.
FORMULATION EXAMPLE 8
Dusts
A mixture of 0.3 part of each of Compound Nos. 6 and 7 and 0.03 part of
fine powders of synthetic hydrated silica is stirred in a mixer and
pulverized by a centrifugal pulverizer. After addition of 2 parts of
fenitrothion, 2.97 parts of fine powders of synthetic hydrated silica, 1
part of "Driless B" and 3.7 parts of clay thereto, the resultant mixture
is pestled in a mortar and stirred in a mixer. Then, 90 parts of cut clay
are added thereto, and the resultant mixture is further mixed in a sack to
give dusts.
FORMULATION EXAMPLE 9
Dusts
A mixture of 0.3 part of each of Compound Nos. 1, 2, 3, 4, 5 and 8, 2 parts
of BPMC (O-sec-butylphenyl N-methylcarbamate) as a carbamate insecticide,
3 parts of fine powders of synthetic hydrated silica, 1 part of "Driless
B" and 3.7 parts of clay are pestled in a mortar and stirred in a mixer.
Then, 90 parts of cut clay are added thereto, and the resultant mixture is
further mixed in a sack to give dusts.
FORMULATION EXAMPLE 10
Dusts
A mixture of 0.3 part of each of Compound Nos. 6, and 7 and 0.03 part of
fine powders of synthetic hydrated silica is stirred in a mixer and
pulverized by a centrifugal pulverizer. After addition of 2 part of BPMC,
2.97 part of fine powders of synthetic hydrated silica, 1 part of "Driless
B" and 3.7 parts of clay thereto, the resultant mixture is pestled in a
mortar and stirred in a mixer. Then, 90 parts of cut clay are added
thereto, and the resultant mixture is further mixed in a sack to give
dusts.
FORMULATION EXAMPLE 11
Dusts
To a solution of 1 part of each of Compound Nos. 1 to 8 in an appropriate
amount of acetone, 5 parts of fine powders of synthetic hydrated silica,
0.3 part of PAP (acidic isopropyl phosphate) and 93.7 parts of clay are
added, and the resultant mixture is stirred in a mixer, followed by
evaporation of acetone to give dusts containing the active ingredient in
1%.
FORMULATION EXAMPLE 12
Flowable Concentrate
To 40 parts of an aqueous solution containing 2 parts of polyvinyl aocohol,
10 parts of each of Compound Nos. 1, 2, 3, 4, 5 and 8 are added, and the
resultant mixture is stirred in a mixer. To the obtained dispersion, 40
parts of an aqueous solution containing 0.05 part of xanthane gum and 0.1
part of aluminum magnesium silicate are added, followed by addition of 10
parts of propylene glycol. The mixture is gently stirred to give a
flowable concentrate containing the active ingredient in 10%.
FORMULATION EXAMPLE 13
Flowable Concentrate
To 28.5 parts of an aqueous solution containing 2 parts of polyvinyl
alcohol, 20 parts of each of Compound Nos. 6 and 7 and 1.5 parts of
sorbitan trioleate are added, and the resultant mixture is finely
pulverized by the aid a sand grinder to give particles of less than 3
microns in average particle size. To the resultant mixture, 40 parts of an
aqueous solution containing 0.05 part of xanthane gum and 0.1 part of
aluminum magnesium silicate are added, followed by addition of 10 parts of
propylene glycol. The mixture is gently stirred to give a flowable
concentrate containing the active ingredient in 20%.
FORMULATION EXAMPLE 14
Oil Spray
Into a mixture of 5 parts of xylene and 5 parts of trichloroethane, 0.1
part of each of Compound Nos. 1 to 8 is dissolved, and the resultant
solution is mixed with 89.9 parts of deodorized kerosene to give an oil
spray containing the active ingredient in 0.1%.
FORMULATION EXAMPLE 15
Oil-Based Aerosol
A solution of 0.1 part of each of Compound Nos. 1 to 8, 0.2 part of
tetramethrin (2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic
acid (1,2,3,4,5,7-hexahydro-1,3-dioxo-2H-isoindol-2-yl)methyl ester) and
0.1 part of d-phenothrin
(2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid
(3-phenoxyphenyl)methyl ester) in a mixture of 10 parts of trichloroethane
and 59.6 parts of deodorized kerosene is filled in an aerosol container.
After provision of a valve, 30 parts of a propellant (liquefied petroleum
gas) is filled through the valve under compression to give an oil-based
aerosol.
FORMULATION EXAMPLE 16
Water-Based Aerosol
A solution of 0.2 part of each of Compound Nos. 1 to 8, 0.2 part of
d-allethrin (2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic
acid 2-methyl-4-oxo-3-(2 -propenyl)-2-cyclopenten-2-yl ester), 0.2 part of
d-phenothrin, 5 parts of xylene, 3.4 parts of deodorized kerosene and 1
part of an emulsifier ("ATMOS 300".RTM., Atlas Chemical Co., Ltd.) in 50
parts of destilled water is filled in an aerosol container. After
provision of a valve, 40 parts of a propellant (liquefied petroleum gas)
is filled through the valve under compression to give a water-based
aerosol.
FORMULATION EXAMPLE 17
Fumigant
Each of Compound Nos. 1 to 8 (100 mg) is dissolved in an appropriate amount
of acetone, and the resultant solution is impregnated with a porous
ceramic plate (4.0.times.4.0.times.1.2 cm) to give a fumigant.
The following Test Examples show some of test results which support the
controlling effect of the 4-substituted-2-chlorophenoxypropylpyrazole
compounds (I) as the active ingredient on insect pests. The compound
numbers correspond to those as shown in Table 1. The compounds used for
comparison are as follows:
TABLE 2
__________________________________________________________________________
Compound
symbol
Chemical structure Remarks
__________________________________________________________________________
##STR15## Compound disclosed in U.S. Pat. No.
4,943,586
B
##STR16## Compound disclosed in U.S. Pat. No.
4,943,586
C
##STR17## Compound disclosed in U.S. Pat. No.
4,943,586
D
##STR18## Compound disclosed in European
EP-A-376,598
E
##STR19## Compound disclosed in European
EP-A-376,598
__________________________________________________________________________
TEST EXAMPLE 1
Metamorphosis Inhibitory Activity Against Brown Rice Planthopper Nymphs
An emulsifiable concentrate prepared according to Formulation Example 1 was
diluted with water to make a predetermined concentration. The dilution was
sprayed onto rice plants cultivated in polyethylene cups at a rate of 20
ml/2 pots on a turning table. After air-drying, the plants were infested
with about ten 3rd instar nymphs of brown rice planthopper (Nilaparvata
lugens). After 10 days, the number of normal adults was counted to obtain
an emergence inhibitory rate. The results are shown in Table 4.
TABLE 3
______________________________________
Compound Inhibitory
No. Concentration (ppm)
rate (%)
______________________________________
1 5 100
0.5 100
2 5 100
0.5 100
0.05 100
3 5 100
0.5 100
0.05 100
4 5 100
0.5 100
0.05 100
5 5 100
0.5 100
0.05 100
6 5 100
0.5 100
0.05 100
7 5 100
0.5 100
0.05 100
8 5 100
0.5 100
A 50 0
5 0
B 50 0
5 35
C 50 90
5 29
D 5 30
0.5 10
E 5 13
0.5 8
______________________________________
TEST EXAMPLE 2
Reproduction Inhibitory Activity Against Green Rice Leafhopper
An emulsifiable concentrate prepared according to Formulation Example 1 was
diluted with water to make a predetermined concentration. The dilution was
sprayed onto rice plants, (about 20 cm in height) cultivated in plastic
polts (1/5000 are in width) at a rate of 40 ml/2 pots on a turning table.
After air-drying, the pots were covered with wire cages, and each 10 male
and female adults of green rice leafhopper (Nephotettix cincticeps) were
released in each of the cages. After 3 weeks, the number of nymphs was
counted to obtain a reproduction inhibitory rate. The results are shown in
Table 4.
TABLE 4
______________________________________
Compound Inhibitory
No. Concentration (ppm)
rate (%)
______________________________________
1 200 100
2 200 100
3 200 100
4 200 100
5 200 100
6 200 100
7 200 100
8 200 100
______________________________________
TEST EXAMPLE 3
Ovicidal Activity Against Greenhouse Whitefly
An emulsifiable concentrate prepared according to Formulation Example 1 was
diluted with water to make a predetermined concentration. Into the
dilution, leaf discs of kidney bean with eggs laid during from 48 hours to
72 hours by aduls of greehouse whitefly (Trialeurodes vaporariorum) were
dipped for 10 seconds. After 7 days, the number of hatchlings was counted
to obtain an ovicidal rate. The results are shown in Table 5.
TABLE 5
______________________________________
Compound Ovicidal
No. Concentration (ppm)
rate (%)
______________________________________
1 10 100
2 10 100
3 10 100
4 10 100
5 10 100
6 10 100
7 10 100
8 10 100
______________________________________
TEST EXAMPLE 4
Reproduction Inhibitory Activity Against Cotton Aphids
An emulsifiable concentrate prepared according to Formulation Example 1 was
diluted with water to make a predetermined concentration. The dilution was
sprayed onto potted cotton plants (in a stage of 8-9 days after sowing)
infested with 1st instar nymphs of cotton aphids (Aphis gossypil) at a
rate of 30 ml/2 pots on a turning table. Before spraying and one week
after spraying, the number of nymphs and aduts was counted, and a
reproduction inhibitory index was expressed by the following equation:
##EQU1##
wherein the judgement of activity is based on the following standard:
______________________________________
A: less than 1 (excellent effect)
B: from 1 to 3 (slight effect)
C: more than 3 (little effect)
D: same as in the untreated pots (no effect)
______________________________________
The results are shown in Table 7.
TABLE 7
______________________________________
Compound Inhibitory
No. Concentration (ppm)
rate
______________________________________
1 100 A
3 100 A
4 100 A
6 100 A
______________________________________
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